Thiocyano aliphatic carboxylic acid esters of hydroxydihydronordicyclopentadiene



Patented Feb. 12, 1946 UNITED STATES PATENT orrics THIOCYANO ALIPHATIC CARBOXYLIC ACID ESTERS OF HYDROXYDIHYDRONORDICY- CLOPENTADIENE Herman A. Bruson, Philadelphia, Pa., assignor, by mesne assignments, to The Resincus Products & Chemical Company, Philadelphia, Pa a corporation of Delaware No Drawing. Application September 12, 1944, Serial No. 5,5330% 4. Claims.

This invention relates to nev esters of thiocyano aliphatic carboxylic acids and of hydroxydihydronordicyclopentadiene. These esters have the generei formula mHnOCOA-SCN wherein CmHl: is the dihydronordicyclopentadiene group and A is an alkyiene radical.

This application is a continuation-in-part of my copending application Serial No. 476,639, filed 1 February 20, 1943, wherein there is broadly disclosed the reaction of carboxylic acids with polycyclopentadienes having two double bonds per molecule in the presence of acidic condensing agents. In this reaction, the acid is added across the double bond of the endomethylene cycle with simultaneous rearrangement of this cycle to an endoethylene cyclopentano system having a cyclopenteno group attached thereto. The new ring system which is thus obtained is herein termed 2o "norpolycyclopentadiene" generically and nordicyclopentadiene specifically for the system derived from dicyclopentadiene. The alcohols which correspond are termed hydroxydihydronorpolycyclopentadiene and hydroxydihydronordicyclopentedlene respectively.

The new compounds of this invention are readily prepared by adding together with rearrangement a halogenated aliphatic carboxylic acid and dicyclopentadiene, preferably in the presence of an acidic condensing agent, to form an ester of hydroxydihydronordicyclopentadiene, and replacing the halogen atom thereof with a thiocyano radical. Alternatively, the new esters of this invention are prepared by esterifying hydroxydihydrcnordicyclopentadiene with a halo carboxylic acid and then replacing the halogen of the resulting ester with a thiocyanate group.

According to the reaction involving both addition and rearrangement dicyclopentadiene reacts (or. zoo-c) with a halogenated fatty acid, XACOOH, where X represents chlorine or bromine, and the resulting product is converted to a thiocyanate as follows:

NCSAOCO-C esters of sulfuric acid such as ethyl acid sulfate,

sulfonic acids such as toluene sulfonic acid or butylsulfonic acid, other strong acids, the usual amphoteric metal halides such as aluminum chloride and the like. The amount of acidic condens- ,ing agent may vary widely from a small percent of the weight of the dicyclopentadiene to a molecular 0 equivalent or more.

The reaction may be performed with or without an inert solvent, such as ethylene dichloride or dioxane. It may be performed at temperatures from room temperature up to 150 C. and more, al-

though the range of 50 C. to about 140 C. is preferred.

The conversion 'of haloester to thiocyano ester may be done according to conventional procedures. For example, the haloester may be taken up in an organic solvent with a salt of thiocyanic acid, such as sodium, potassium, calcium, barium, ammonium, or lead thiocyanates, and the mixture heated and stirred. The halogen salt, which is formed by metathesis, is readily separated from the reaction product and the thiocyano ester I worked up bysuch method as treatment with charcoal, solvent extraction, distillation, etc.

In the alternativ procedure mentioned above,

boxylic osjatty acids. Of these, the acids having two eight carbon atoms form a preferred class.

The new thiocyano aliphatic carboxylic acid esters of hydroxydihydronordicyclopentadiene are generally liquids and have a high degree of solubility in hydrocarbon solvents. The esters of acids of one to four carbon atoms are particularly valuable as toxicants for insecticides.

They may be used in lubricating oil for imparting increased resistance to wear, preventing.

corrosion, and stabilizing the oils.

The following examples illustrate this invention:

Example 1 (a) A mixture of 264 parts of dicyclopentadl- ,ene and 800 parts of aqueous 25% sulfuric acid was stirred rapidly and heated under a reflux condenser at 104-107" C. for 4 /2 hours.v The aqueous sulfuric acid layer was then separated and the oil layer washed successively with hot water, dilute soda solution, and finally again with hot water. The oil was dried and distilled in vacuo at 6 mm. absolute pressure of mercury. The.

product which distilled over between 105 and 115 C./6 mm. was hydroxydihydronordicyclopentadiene. It was a vviscid colorless oil. The yield was 250'parts or 83.4% of theory.

A" mixture of 150 grams of this alcohol, 95 grams of chloroacetic acid, 200 grams of benzene and 1 gram of 40% sulfuric acid was boiled under a reflux condenser attached to a water separator until water ceased coming over. This required about two hours. The product was cooled, washed with water, dried, and. distilled in vacuo to yield 207 grams of the chloroacetate of hydroxydihydronordicyclopentadiene as a colorless liquidboiling at 118-120 C./0.5 mm.

(b) A mixture of.132 grams of dicyclopentadiene, 132 grams of chloroacetic acid and grams of 40% sulfuric acid was stirred for 12 hours at 95 C. The product was washed with dilute soda solution and then with water, dried, and distilled in vacuo to give a 90% yield of the choloracetate 2,894,584 y y I or hydroxydihydronordicyclopentadiene having the following constants:

Boiling point, 154-156 C./10 mm.; n 1.5111; d4 1.1916.

(c) Thereupon 205 grams of the chloroacetate oi. hydroxydihydronordicyclopentadiene as prepared in (a) and in (b) above, 200 grams of ethanol (95%), and 81 grams of sodium thiocyanate was boiled under reflux for 12-15 hours. The

product was cooled, washed thoroughly with way The resulting ter, and the oil distilled in vacuo. vthiocyanoacetate of hydroxydihydronordicyclopentadiene distilled over at 165-168 .C./0.-5 mm.

. as a faintly yellow liquid having a faint not unpleasant odor and having the probable formula on cm cn l l H! H Ncscmcoo-oE A 5% solution in deodorized kerosene when tested as an insecticide against flies gave a 100% knockdown and 100% kill. It may also be used against mosquitoes and other insect pests.

Example 2 95 C. for 4 hours, and after being cooled, washed 40 pentadiene.

, with water and soda solution. The product was then dried in vacuo. The oil obtained amounted to 224 grams and consisted essentially of the pchloropropionate of hydroxydihydronordicyclo- Upon distillation in vacuo the pure compound distills over at -135 C./mm. as a colorless oil.

A mixture of 200 grams or ethanol, 65 grams of sodium thiocyanate and 157 grams of the above 'B-chloropropionate o! hydroxydihydronordicyclopentadiene was boiled under reflux for 17 hours. The product was washed thoroughly with water and dried in vacuo to yield 168 grams of crude p-thiocyanopropionate oi. ,hydroxydihydronordicyclopentadiene as an amber-colored oil having the probable formula NCSOHxCHaCO O It is particularly useful in fly sprays alone or with pyrethrum or rotenone as an insecticide.

Example 3 hydroxydihydronordicyclopentadiene is obtained as an amber-colored oil which can be used as a toxicant for the preparation of insecticides,

I claim:

Upon distillation in vacuo it boiled at 167-174 C./0.5 mm. and formed a viscous pale yellow oil. 1

5 tadiene.

onlc acid ester-of hydroxydihydronordlcyclopen tadiene. 4. As a new compound, the a-thiocyano isobutyric acid ester 0! hydroxydihydronordicyclopen- HERMAN A. BRUSON. v 

